DFG（プロジェクトSM 82 / 13-1）からの財政支援を深く感謝されています。

アミド化ペクチン原液の調製<ol><li> 980グラムの水（2.0重量％）で20グラムアミド化ペクチンを混ぜます。アミド化の程度は、25重量％です。 </li><li>均一な粘性溶液を得るために2分間高速攪拌機（10,000 rpm）以上の溶液を均質化します。 </li><li> pHはストリップまたはpHメーターを用いてpHを測定します。 pHが6.5未満である場合には、液（pH 7.0）溶液を中和するために0.5 M NaOHで滴定します。 </li><li>ドライアミド化ペクチン（Q = 1）のグラム当たり0.1825グラムの割合で炭酸カルシウムを追加します。 「Q」は、架橋度を示します。 </li><li> 1キロ2.0重量％アミド化ペクチン溶液、20.0グラムの乾燥ペクチンあたり3.65グラムの炭酸カルシウム（Q = 1）7を追加します。 </li><li>大きい架橋には、乾燥したアミド化ペクチン（Q = 2）のグラム当たり0.3650グラムの炭酸カルシウムを追加します。 </li></ol>ヒドロゲルの2.生産<ol><li>得るために、高速ホモジナイザー（10,000 rpm）を用いてアミド化ペクチン/炭酸カルシウム混合物を均質化白の均一な分散液。 </li><li>オープンポリプロピレン型またはガラスペトリ皿にサスペンションを転送します。 </li><li>高圧オートクレーブ中で金型を置きます。オートクレーブを密封します。 </li><li> RTで5 MPaのまでのガス状のCO 2とオートクレーブを加圧します。 Gurikov らを参照してください。7の詳細については。 24時間のための圧力を維持します。 </li><li>ゆっくりは0.2MPa / minでオートクレーブを減圧。 </li><li>オートクレーブを開き、金型を削除します。それらを裏返しすることにより金型からヒドロゲルを削除します。必要であれば、スパチュラを使用しています。 </li></ol> 3.溶媒交換手順<ol><li> 10:90 10gを調製したヒドロゲルのグラム当たりのエタノール/水混合物（w / w）です。 </li><li> 12時間10:90（w / w）のエタノール/水混合物中にヒドロゲルを浸します。 </li><li> つまり 、エタノール濃度の増加に伴って、このプロセスを続行し、10：90から（w / w）のエタノール/水混合物30:70（w / w）のエタノール/水混合物。 12時間後、5への転送0時50分、70：30（12時間）の後、エタノール/水混合物は、90：10（12時間）、次いで100％エタノール溶液（12時間）（w / w）です。 </li><li>ゲル内部の最終濃度が98％以上（重量/重量）となるように純エタノールでさらにゲルを浸します。密度計を用いて濃度を測定します。アルコゲルは現在、超臨界CO 2乾燥のための準備ができています。 </li></ol>超臨界CO 2乾燥によるエアロゲルの4生産<ol><li>ヒドロゲルの調製のために使用したのと同じ高圧オートクレーブにサンプルを配置し（ステップ2.3参照）。 </li><li>ゲルから早期の溶媒の蒸発を防ぐために、追加のエタノール（オートクレーブ量2〜10％）でオートクレーブを埋めます。溶媒中のゲルの完全な浸漬は必要ありません。 </li><li>オートクレーブを密封します。オートクレーブ加熱をオンにします。 323 K.加圧し、圧縮機またはポンプを使用して、12 MPaでの二酸化炭素でオートクレーブに、オートクレーブ作業温度を設定します。 </li><li>定期的にCO 2を置き換えます新鮮なCO 2の圧力を一定に保ちながらオートクレーブ10,11内部。 6-7滞留ボリュームは6時間の期間にわたって必要とされます。 Gurikov らを参照してください。7の詳細については。 </li><li>ゆっくりは0.2MPa / minでオートクレーブを減圧。 </li><li>オートクレーブを開き、エアロゲルを収集します。 exicatorまたは密閉容器内のエアロゲルを保管してください。 </li></ol>

<ol>
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著者は、彼らが競合する金融利害関係を持たないことを宣言します。

CO 2誘発性ゲル化技術を用いて、一つはバイオポリマーの架橋を誘導するために必要な（例えば、酢酸またはグルコノラクトン（GDL）のために）化学代替の必要性を排除することができます。アミド化ペクチンエーロゲルの表面積は、しかしながら、細孔容積が文献5に示されたものよりもはるかに高い、文献値5より高い範囲にあります。高い細孔容積は、また、CO 2誘導性のゲル化7によって調製アルギン酸エアロゲルを観察しました。しかし、この高い細孔容積（4-150 nmの細孔サイズ範囲）の理由は、ゲル化法、または以前に文献で取り上げられていないバイオポリマーの固有の特性によるものであるかどうかを検証されていません。ペクチンエアロゲルは特性12を superinsulating有することが文献に報告されており、この技術により調製アルギン酸エアロゲルはまた、superinsulatingの範囲内の熱伝導率を有し3,7。従って、この技術によって製造さアミド化ペクチンエアロゲルもsuperinsulating特性を有することが考えられます。 プロトコルの第2節での減圧の速度は、ヒドロゲルの準備の重要なステップです。高速減圧は、ゲルの増加マクロ多孔性につながることができます。この現象は、相互接続性を有する材料のマクロ多孔性は、細胞13,14の成長および増殖のために重要な特徴である組織工学用途に適用することができます。また、プロトコルの第1中の架橋度は、シネレシスにおいて重要な役割を果たし、アミド化ペクチンヒドロゲルの膨潤性。これは、その膨潤挙動ならびに15架橋剤の濃度によって影響されるアルギン酸ハイドロゲルに似ています。これによりアミド化ペクチン製エアロゲルはまた、アルギン酸塩エアロゲル16について報告されたものと同様の超吸収特性を有するように調整することができます。 &lt;プライマリシステムとしてアミド化ペクチン（又はアルギン酸塩）を考慮CO 2誘発性ゲルを使用することにより= &quot;jove_content「Pクラス&gt;、さらなる多様性は、異なる架橋剤とバイオポリマーの組み合わせを導入することにより、エアロゲル中に組み込むことができます。いくつかの金属炭酸塩（ 例えば、亜鉛、ニッケル、コバルト、銅、ストロンチウム、バリウム）は、カチオンは、加圧CO 2（3~5 MPa）とを用いて水性媒体中でpH低下によって解放することができる3の架橋のために使用することができます。しかし、これらのカチオンのいくつかの不溶性塩は、より低い生体高分子濃度について安定な分散体を形成しないことがあり、不均一なゲルにつながる底に落ち着くことができます。これは、CO 2誘導性のゲル3を含む内部設定ゲル化法と一般的な問題であり、これにより、アプリケーションのための技術のユーザビリティは、ケースケースに基づいて評価されるべきです。 種々の配合物は、水溶性の生体を用いて調製し例えば、デンプン、カラギーナン、メチルおよびカルボキシメチルセルロース、ジェランガム、リグニン、ゼラチンなどのようなポリマー;ポリエチレングリコール（PEG）、ポリビニルアルコール（PVA）、プルロニックP-123などのような水溶性の合成ポリマー;このようなケイ酸ナトリウム等の水溶性の無機前駆体はまた、調節可能な特性を有する2アルギン酸同様のハイブリッドエアロゲルを製造するためにアミド化ペクチンと混合することができます。 超臨界CO 2乾燥（SCCO 2乾燥）エアロゲル製造において典型工程、CO 2 17,18またはゲルを使用して、このような溶媒交換や乾燥などの前処理工程の任意の組み合わせであるように、CO 2 7を用いて溶媒交換および乾燥を提供することができクリア処理の利点。バイオポリマー分散液は、単一のオートクレーブ中で、メイン処理媒体としてCO 2を使用してバイオポリマーエアロゲルに変換することができる。利点は、集積ワンポット法として想定されます。ためにゲル化、溶媒交換、超臨界乾燥および処理媒体としてCO 2を使用して、単一のオートクレーブ内で5,19プロセスをロードする活性成分：特定の医薬用途は、1は、4つのステップを実行するも想像することができます。特定の場合には、そのような薬剤を負荷したエアロゲルの保護コーティングとしての後処理は、標的薬剤放出20のために必要です。 結論として、本研究は、アミド化ペクチンベースのシステムのゲル化のための加圧CO 2の使用方法を示しています。また、単一のオートクレーブ内のターゲット・アプリケーションのための製品への変換前駆体のための一般的な媒体としての加圧CO 2の使用が想定されます。

エアロゲルは、（例えば、シリカ、チタニア、ジルコニアなどのような）無機（例えば、レゾルシノールホルムアルデヒド、ポリウレタン等のような）合成または生体高分子（多糖類、タンパク質および他の範囲の前駆体の様々な方法を用いて調製することができる多孔性物質のクラスであります）2。どのような従来の多孔性材料からそれらを離れて設定すると、同時に3つのすべての特性を有するための能力です。即ち、高表面積、超低密度メソポーラス細孔径分布（ すなわち 、2〜50ナノメートルの孔サイズ）。前述の特性により、エアロゲルは広く断熱、生物医学、触媒、吸着と吸収用途、医薬品およびneutraceuticals 2の分野で応用されています。上記の可能性を考慮すると、生体高分子ゲルシステムの生産及びエアロゲルへのその後の変換は、バイオベースの高付加価値の方の機会を多数開きます材料。このような努力は、一例として、アミド化ペクチンを使用して、この研究に取りました。 エアロゲルは、典型的には、ゾル - ゲル法により製造されます。ゲルは、マトリックス中に捕捉された液体からなるシステムであり、熱または低温クロス3を連結する共有結合、イオン結合、pHを誘発さによって調製することができます。この特定のシステムのために、私たちはイオン架橋を利用して、 すなわち、二価カチオン（ 例えば 、カルシウム）を一緒に生体高分子鎖を架橋します。そのようなアミド化ペクチンやアルギン酸などの生体高分子の制御可能なイオン架橋を行うためには、拡散法や内部設定方法4を使用することができます。陽イオンがアミド化ペクチンやアルギン酸の液滴又は層4に外溶液から拡散するように拡散法では、ゲル化は、拡散伝播が続く外側の層で、最初に発生します。内部設定方法では、架橋剤の不溶性形態は、均質バイオポリマーsolutioに分散されていますnおよびカチオンはpH変化4,5,6を開始することによって解放されます。しかし、両方の技術は、スラブまたはモノリシック形で産生された場合、最終的なゲルの均質性に関する問題に直面しています。この作品は、アルギン酸塩ゲル3,7上の以前の作品にさらなる構築アミド化ペクチンヒドロゲルを製造するための高圧CO 2（5メガパスカル）の使用方法を示します。簡潔には、均一なゲルを生成する代わりに弱酸のpHを減少させるために加圧されたCO 2を利用して内部設定ゲル化技術です。圧力の増加に伴って、水が上昇中の二酸化炭素の溶解度は、3.0〜8のpHの低下を伴います。これは、カルシウムイオンを放出し、炭酸カルシウムが可溶化させます。カルシウムイオンは、ヒドロゲルを生成するアミド化ペクチンバイオポリマーと架橋します。非常に低い生体高分子の濃度（0.05重量％）までの安定した均質なゲルは、この技術7を使用して製造することができました。 gelatとしてイオンは、水性媒体中で行われ、有機溶媒への溶媒交換を伴うCO 2 /水系中で混和性ギャップに必要とされます。典型的には低分子量アルコール（メタノール/エタノール/イソプロパノール）、ケトン類（アセトン）を溶媒交換処理に用いることができます。しかし、純粋なエタノール又は他の有機溶媒と一緒にお風呂での直接浸漬は、重大な不可逆的な収縮につながります。この欠点を回避するために、段階的な溶媒交換は5,9行われます。ゲル内部の溶媒濃度が&gt; 98％に達すると、有機溶媒がエアロゲルを残し、超臨界CO 2（12メガパスカル）で乾燥します。

<table border="0" cellpadding="0" cellspacing="0" width="1321">
	<tbody>
		<tr height="26">
			<td height="26" style="height:26px;width:289px;">Equipment</td>
			<td style="width:196px;"></td>
			<td style="width:240px;"></td>
			<td style="width:596px;"></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Ultraturrax homogenizer</td>
			<td>IKA, Germany</td>
			<td>T 25 Digital</td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Polypropylene molds</td>
			<td>TH. Geyer, Germany</td>
			<td>9,033,201</td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">High pressure autoclave&#160;</td>
			<td>Ernst Haage, Germany</td>
			<td>custom made</td>
			<td>Setup constuction done in-house</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Compressor</td>
			<td>Andreas Hofer</td>
			<td>MKZ 185-40</td>
			<td>Setup constuction done in-house</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Nitrogen adsorption</td>
			<td>Quantachrome</td>
			<td>Nova 4000e</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Density meter</td>
			<td>Anton Paar</td>
			<td>DMA 4000</td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Name</td>
			<td>Company</td>
			<td>Catalog Number</td>
			<td>Comments</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;width:289px;">Chemicals</td>
			<td style="width:196px;"></td>
			<td style="width:240px;"></td>
			<td></td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Amidated pectin</td>
			<td>Herbstreith and Fox, Germany</td>
			<td>CU 025</td>
			<td>CAS # 56645-02-4; provided by company for research purposes</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Sodium Hydroxide</td>
			<td>Sigma Aldrich, Germany</td>
			<td style="width:240px;">S8045</td>
			<td>CAS # 1310-73-2; required only in case the pectin solution needs to be neutralized to pH 6.5-7.5</td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Calcium carbonate</td>
			<td>Magnesia GmbH, Germany</td>
			<td style="width:240px;">4421 Calcium carbonat, leicht, pr&#228;zipitiert, EP, E170</td>
			<td>CAS # 471-34-1</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Ethanol, 99.8 %</td>
			<td>Sigma Aldrich, Germany</td>
			<td>32205</td>
			<td>CAS # 64-17-5</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Carbon dioxide, 99.9 %</td>
			<td>AGA Gas GmbH, Germany</td>
			<td></td>
			<td>CAS # 124-38-9; in-house tank available (3 ton)</td>
		</tr>
		<tr height="20">
			<td height="20" style="height:20px;">Deionised Water</td>
			<td></td>
			<td></td>
			<td>CAS # 7732-18-5;&#160; available in-house (6.4-7.0 pH)</td>
		</tr>
	</tbody>
</table>

preparation of biopolymer aerogels using green solvents

Although the first reports on aerogels made by Kistler1 in the 1930s dealt with aerogels from both inorganic oxides (silica and others) and biopolymers (gelatin, agar, cellulose), only recently have biomasses been recognized as an abundant source of chemically diverse macromolecules for functional aerogel materials. Biopolymer aerogels (pectin, alginate, chitosan, cellulose, etc.) exhibit both specific inheritable functions of starting biopolymers and distinctive features of aerogels (80-99% porosity and specific surface up to 800 m2/g). This synergy of properties makes biopolymer aerogels promising candidates for a wide gamut of applications such as thermal insulation, tissue engineering and regenerative medicine, drug delivery systems, functional foods, catalysts, adsorbents and sensors. This work demonstrates the use of pressurized carbon dioxide (5 MPa) for the ionic cross linking of amidated pectin into hydrogels. Initially a biopolymer/salt dispersion is prepared in water. Under pressurized CO2 conditions, the pH of the biopolymer solution is lowered to 3 which releases the crosslinking cations from the salt to bind with the biopolymer yielding hydrogels. Solvent exchange to ethanol and further supercritical CO2 drying (10 - 12 MPa) yield aerogels. Obtained aerogels are ultra-porous with low density (as low as 0.02 g/cm3), high specific surface area (350 - 500 m2/g) and pore volume (3 - 7 cm3/g for pore sizes less than 150 nm).

（プロトコル部2に指示されるように）より高い架橋度（Q = 2）でゲル化工程後に得られた代表的なヒドロゲルは、図1に示されている。左側の試料（試料A及びB）が2重量％と1重量％ですCO 2誘導性のゲル化により得られたペクチンゲル。バイオポリマーの濃度（0.5重量％以下）を減少させることにより、ゲルは透明（試料C）となります。生体高分子の濃度（0.25重量％）のさらなる減少はまた、安定したヒドロゲル（試料D）が得られるが、これらのゲルは非常に壊れやすく、取り扱いの際に破ることができます。溶解したCO 2は、CO 2の溶解度の減少によるゲル水システムを離れるとヒドロゲルの内側に観察された気泡は減圧時に作成されます。 アミド化ペクチンエアロゲル特性を表1に示す。得られたエアロゲルは、低デン有する超多孔質であります<html> sityエアロゲルの質量と体積の比として測定した（3グラム / cmの0.013という低いです）。表面積は、窒素吸着によって測定されます。 500 2 / gの-ペクチンエアロゲルの場合は、350の間の特定の表面積を生じました。 4-150ナノメートルの範囲の細孔サイズの細孔容積は、窒素（BJH法）を用いて細孔充填のケルビンモデルによって測定されます。 4と150 nmの細孔サイズのために7センチメートル3 /グラム-アミド化ペクチンエアロゲルのための細孔容積は3の間でした。 <img alt="図1" src="/files/ftp_upload/54116/54116fig1.jpg" /> 高い架橋度（Q = 2）図1.アミド化ペクチンヒドロゲル左上：2重量％（サンプルA）;。右上：1重量％（試料B）。下左：0.5重量％（サンプルC）を、右下：0.25重量％（試料D）。ゲルは、バイオポリマーの濃度を低下させると透明になります。気泡はCO 2減圧中に生成されます。https://www.jove.com/files/ftp_upload/54116/54116fig1large.jpg &quot;ターゲット=&quot; _空白 &quot;&gt;この図の拡大版をご覧になるにはこちらをクリックしてください。 <table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always"><tbody><tr><td> ペクチン濃度[重量％] </td><td> 架橋度Q </td><td> 嵩密度[グラム/ cm 3の] </td><td> 比表面積[m 2の/ G] </td><td> 比細孔体積[cm 3の/ G] </td><td> 平均孔径（直径）[nm]で </td></tr><tr><td> 2.00 </td><td> 1 </td><td> 0.081 </td><td> 502 </td><td> 4.1 </td><td> 14 </td></tr><tr><td> 1.00 </td><td> 1 </td><td> 0.044 </td><td> 491 </td><td> 7.1 </td><td> 27 </td></tr><tr><td> 0.50 </td><td> 1 </td><td> 0.035 </td><td> 357 </td><td> 3.8 </td><td> 27 </td></tr><tr><td> 0.25 </td><td> 1 </tD&gt; <td> 0.013 </td><td> 335 </td><td> 4.9 </td><td> 41 </td></tr><tr><td> 2.00 </td><td> 2 </td><td> 0.069 </td><td> 447 </td><td> 3.1 </td><td> 13 </td></tr><tr><td> 1.00 </td><td> 2 </td><td> 0.048 </td><td> 441 </td><td> 3.6 </td><td> 26 </td></tr><tr><td> 0.50 </td><td> 2 </td><td> 0.030 </td><td> 429 </td><td> 5.8 </td><td> 25 </td></tr><tr><td> 0.25 </td><td> 2 </td><td> 0.017 </td><td> 347 </td><td> 5.0 </td><td> 24 </td></tr></tbody></table> 表アミド化ペクチンエアロゲルの1特徴。

Watch this Scientific Journal Video about Preparation of Biopolymer Aerogels Using Green Solvents at JoVE.com

Preparation of Biopolymer Aerogels Using Green Solvents

A new way for the production of biopolymer-based aerogels by carbon dioxide (CO2) induced gelation is shown. The technique utilizes pressurized carbon dioxide (5 MPa) for the production of biopolymer hydrogels and supercritical CO2 (12 MPa) to convert gels into aerogels. The only solvents needed besides CO2 are water and ethanol.

グリーン溶剤を使用したバイオポリマーエアロゲルの調製

Although the first reports on aerogels made by Kistler1 in the 1930s dealt with aerogels from both inorganic oxides (silica and others) and biopolymers ...

preparation-of-biopolymer-aerogels-using-green-solvents

Research

JoVE Journal

Chemistry

17.5K ビュー.  Hamburg University of Technology. A new way for the production of biopolymer-based aerogels by carbon dioxide (CO2) induced gelation is shown. The technique utilizes pressurized carbon dioxide (5 MPa) for the production of biopolymer hydrogels and supercritical CO2 (12 MPa) to convert gels into aerogels. The only solvents needed besides CO2 are water and ethanol.

ビデオ: Preparation of Biopolymer Aerogels Using Green Solvents

Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow

While the first Electron Paramagnetic Resonance (EPR) studies regarding the effects of oxidation on the structure and stability of carbon radicals date back to the early 1980s the focus of these early papers primarily characterized the changes to the structures under extremely harsh conditions (pH or temperature)1-3. It is also known that paramagnetic molecular oxygen undergoes a Heisenberg spin exchange interaction with stable radicals that extremely broadens the EPR signal4-6. Recently, we reported interesting results where this interaction of molecular oxygen with a certain part of the existing stable radical structure can be reversibly affected simply by flowing a diamagnetic gas through the carbon samples at STP7. As flows of He, CO2, and N2 had a similar effect these interactions occur at the surface area of the macropore system.
This manuscript highlights the experimental techniques, work-up, and analysis towards affecting the existing stable radical nature in the carbon structures. It is hoped that it will help towards further development and understanding of these interactions in the community at large.

Stable radicals that are present in carbon substrates interact with paramagnetic oxygen through a Heisenberg spin exchange. This interaction can be significantly reduced under STP conditions by flowing a diamagnetic gas over the carbon system. This manuscript describes a simple method to characterize the nature of those radicals.

電子常磁性共鳴とキャリブレーション済みのガスの流れによってカーボン表面のラジカル自然を探る

While the first Electron Paramagnetic Resonance (EPR) studies regarding the effects of oxidation on the structure and stability of carbon radicals date ...

化学

Real-time Monitoring of Reactions Performed Using Continuous-flow Processing: The Preparation of 3-Acetylcoumarin as an Example

By using inline monitoring, it is possible to optimize reactions performed using continuous-flow processing in a simple and rapid way. It is also possible to ensure consistent product quality over time using this technique. We here show how to interface a commercially available flow unit with a Raman spectrometer. The Raman flow cell is placed after the back-pressure regulator, meaning that it can be operated at atmospheric pressure. In addition, the fact that the product stream passes through a length of tubing before entering the flow cell means that the material is at RT. It is important that the spectra are acquired under isothermal conditions since Raman signal intensity is temperature dependent. Having assembled the apparatus, we then show how to monitor a chemical reaction, the piperidine-catalyzed synthesis of 3-acetylcoumarin from salicylaldehyde and ethyl acetoacetate being used as an example. The reaction can be performed over a range of flow rates and temperatures, the in-situ monitoring tool being used to optimize conditions simply and easily.

Real-time monitoring allows for fast optimization of reactions performed using continuous-flow processing. Here the preparation of 3-acetylcoumarin is used as an example. The apparatus for performing in-situ Raman monitoring is described, as are the steps required to optimize the reaction.

連続フロー処理を​​使用して行われる反応のリアルタイムモニタリング：例として3- Acetylcoumarinの調製

By using inline monitoring, it is possible to optimize reactions performed using continuous-flow processing in a simple and rapid way. It is also possible ...

Synthetic Methodology for Asymmetric Ferrocene Derived Bio-conjugate Systems via Solid Phase Resin-based Methodology

Early detection is a key to successful treatment of most diseases, and is particularly imperative for the diagnosis and treatment of many types of cancer. The most common techniques utilized are imaging modalities such as Magnetic Resonance Imaging (MRI), Positron Emission Topography (PET), and Computed Topography (CT) and are optimal for understanding the physical structure of the disease but can only be performed once every four to six weeks due to the use of imaging agents and overall cost. With this in mind, the development of &#8220;point of care&#8221; techniques, such as biosensors, which evaluate the stage of disease and/or efficacy of treatment in the clinician&#8217;s office and do so in a timely manner, would revolutionize treatment protocols.1 As a means to exploring ferrocene based biosensors for the detection of biologically relevant molecules2, methods were developed to produce ferrocene-biotin bio-conjugates described herein. This report will focus on a biotin-ferrocene-cysteine system that can be immobilized on a gold surface.

The synthesis of asymmetric species of ferrocene is challenging using solution techniques. This report focuses on the methods carried out to produce a ferrocene-biotin bioconjugate using facile and clean reactions accomplished via solid-phase synthesis. Incorporation of a thiolate moiety is shown to impart the ability for immobilization on gold surfaces.

固相樹脂系の方法論を経由して、非対称フェロセン派生バイオコンジュゲートシステムのための合成方法論

Early detection is a key to successful treatment of most diseases, and is particularly imperative for the diagnosis and treatment of many types of cancer. ...

Characterization, Quantification and Compound-specific Isotopic Analysis of Pyrogenic Carbon Using Benzene Polycarboxylic Acids (BPCA)

Fire-derived, pyrogenic carbon (PyC), sometimes called black carbon (BC), is the carbonaceous solid residue of biomass and fossil fuel combustion, such as char and soot. PyC is ubiquitous in the environment due to its long persistence, and its abundance might even increase with the projected increase in global wildfire activity and the continued burning of fossil fuel. PyC is also increasingly produced from the industrial pyrolysis of organic wastes, which yields charred soil amendments (biochar). Moreover, the emergence of nanotechnology may also result in the release of PyC-like compounds to the environment. It is thus a high priority to reliably detect, characterize and quantify these charred materials in order to investigate their environmental properties and to understand their role in the carbon cycle.
Here, we present the benzene polycarboxylic acid (BPCA) method, which allows the simultaneous assessment of PyC&#39;s characteristics, quantity and isotopic composition (13C and 14C) on a molecular level. The method is applicable to a very wide range of environmental sample materials and detects PyC over a broad range of the combustion continuum, i.e., it is sensitive to slightly charred biomass as well as high temperature chars and soot. The BPCA protocol presented here is simple to employ, highly reproducible, as well as easily extendable and modifiable to specific requirements. It thus provides a versatile tool for the investigation of PyC in various disciplines, ranging from archeology and environmental forensics to biochar and carbon cycling research.

Characterization, Quantification and Compound-specific Isotopic Analysis of Pyrogenic Carbon Using Benzene Polycarboxylic Acids BPCA

We present the benzene polycarboxylic acid (BPCA) method for assessing pyrogenic carbon (PyC) in the environment. The compound-specific approach uniquely provides simultaneous information about the characteristics, quantity and isotopic composition (13C and 14C) of PyC.

特徴づけ、定量化およびベンゼンポリカルボン酸を使用した熱分解炭素の化合物固有の同位体分析（BPCA）

Fire-derived, pyrogenic carbon (PyC), sometimes called black carbon (BC), is the carbonaceous solid residue of biomass and fossil fuel combustion, such as ...

Green and Low-cost Production of Thermally Stable and Carboxylated Cellulose Nanocrystals and Nanofibrils Using Highly Recyclable Dicarboxylic Acids

Here we demonstrate potentially low cost and green productions of high thermally stable and carboxylated cellulose nanocrystals (CNCs) and nanofibrils (CNF) from bleached eucalyptus pulp (BEP) and unbleached mixed hardwood kraft pulp (UMHP) fibers using highly recyclable dicarboxylic solid acids. Typical operating conditions were acid concentrations of 50 - 70 wt% at 100 &#176;C for 60 min and 120 &#176;C (no boiling at atmospheric pressure) for 120 min, for BEP and UMHP, respectively. The resultant CNCs have a higher thermal degradation temperature than their corresponding feed fibers and carboxylic acid group content from 0.2 - 0.4 mmol/g. The low strength (high pKa of 1.0 - 3.0) of organic acids also resulted in CNCs with both longer lengths of approximately 239 - 336 nm and higher crystallinity than CNCs produced using mineral acids. Cellulose loss to sugar was minimal. Fibrous cellulosic solid residue (FCSR) from the dicarboxylic acid hydrolysis was used to produce carboxylated CNFs through subsequent mechanical fibrillation with low energy input.

Here we demonstrate a novel method for green and sustainable productions of highly thermally stable and carboxylated cellulose nanocrystals (CNC) and nanofibrils (CNF) using highly recyclable solid dicarboxylic acids.

緑とリサイクル性の高いジカルボン酸を使用して熱的に安定したカルボキシル化セルロースナノ結晶とナノフィブリルの低コスト生産

Here we demonstrate potentially low cost and green productions of high thermally stable and carboxylated cellulose nanocrystals (CNCs) and nanofibrils ...

Preparation and Evaluation of 99mTc-labeled Tridentate Chelates for Pre-targeting Using Bioorthogonal Chemistry

Pre-targeting combined with bioorthogonal chemistry is emerging as an effective way to create new radiopharmaceuticals. Of the methods available, the inverse electron demand Diels-Alder (IEDDA) cycloaddition between a radiolabeled tetrazines and trans-cyclooctene (TCO) linked to a biomolecule has proven to be a highly effective bioorthogonal approach to imaging specific biological targets. Despite the fact that technetium-99m remains the most widely used isotope in diagnostic nuclear medicine, there is a scarcity of methods for preparing 99mTc-labeled tetrazines. Herein we report the preparation of a family of tridentate-chelate-tetrazine derivatives and their Tc(I) complexes. These hitherto unknown compounds were radiolabeled with 99mTc using a microwave-assisted method in 31% to 83% radiochemical yield. The products are stable in saline and PBS and react rapidly with TCO derivatives in vitro. Their in vivo pre-targeting abilities were demonstrated using a TCO-bisphosphonate (TCO-BP) derivative that localizes to regions of active bone metabolism or injury. In murine studies, the 99mTc-tetrazines showed high activity concentrations in knees and shoulder joints, which was not observed when experiments were performed in the absence of TCO-BP. The overall uptake in non-target organs and pharmacokinetics varied greatly depending on the nature of the linker and polarity of the chelate.

Preparation and Evaluation of 99mTc-labeled Tridentate Chelates for Pre-targeting Using Bioorthogonal Chemistry

Here, we describe a protocol for radiolabeling and in vivo testing of tridentate 99mTc(I) chelate-tetrazine derivatives for pre-targeting and bioorthogonal chemistry.

の調製と評価<sup&gt; 99メートル</sup&gt; Tc標識三座キレートバイオ直交化学反応を用いて事前ターゲティングするため

Pre-targeting combined with bioorthogonal chemistry is emerging as an effective way to create new radiopharmaceuticals. Of the methods available, the ...

Fabrication and Testing of Catalytic Aerogels Prepared Via Rapid Supercritical Extraction

Protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms are presented. Three preparation methods are described: (a) the incorporation of metal salts into silica or alumina wet gels using an impregnation method; (b) the incorporation of metal salts into alumina wet gels using a co-precursor method; and (c) the addition of metal nanoparticles directly into a silica aerogel precursor mixture. The methods utilize a hydraulic hot press, which allows for rapid (&#60;6 h) supercritical extraction and results in aerogels of low density (0.10 g/mL) and high surface area (200-800 m2/g). While the work presented here focuses on the use of copper salts and copper nanoparticles, the approach can be implemented using other metal salts and nanoparticles. A protocol for testing the three-way catalytic ability of these aerogels for automotive pollution mitigation is also presented. This technique uses custom-built equipment, the Union Catalytic Testbed (UCAT), in which a simulated exhaust mixture is passed over an aerogel sample at a controlled temperature and flow rate. The system is capable of measuring the ability of the catalytic aerogels, under both oxidizing and reducing conditions, to convert CO, NO and unburned hydrocarbons (HCs) to less harmful species (CO2, H2O and N2). Example catalytic results are presented for the aerogels described.

Here we present protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms. Methods for preparing materials using copper salts and copper-containing nanoparticles are featured. Catalytic testing protocols demonstrate the effectiveness of these aerogels for three-way catalysis applications.

急速な超臨界抽出法によって作製した触媒のエアロゲルの作製と試験

Protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms are presented. Three ...

Preparation of Functional Silica Using a Bioinspired Method

The goal of the protocols described herein is to synthesize bioinspired silica materials, perform enzyme encapsulation therein, and partially or totally purify the same by acid elution. By combining sodium silicate with a polyfunctional bioinspired additive, silica is rapidly formed at ambient conditions upon neutralization. 
The effect of neutralization rate and biomolecule addition point on silica yield are investigated, and biomolecule immobilization efficiency is reported for varying addition point. In contrast to other porous silica synthesis methods, it is shown that the mild conditions required for bioinspired silica synthesis are fully compatible with the encapsulation of delicate biomolecules. Additionally, mild conditions are used across all synthesis and modification steps, making bioinspired silica a promising target for the scale-up and commercialization as both a bare material and active support medium.
The synthesis is shown to be highly sensitive to conditions, i.e., the neutralization rate and final synthesis pH, however tight control over these parameters is demonstrated through the use of auto titration methods, leading to high reproducibility in reaction progression pathway and yield. 
Therefore, bioinspired silica is an excellent active material support choice, showing versatility towards many current applications, not limited to those demonstrated here, and potency in future applications.

Here, we present a protocol to synthesize bioinspired silica materials and immobilize enzymes therein. Silica is synthesized by combining sodium silicate and an amine &#39;additive&#39;, which neutralize at a controlled rate. Material properties and function can be altered either by in situ enzyme immobilization or post-synthetic acid elution of encapsulated additives.

バイオインスパイアード法を用いた機能性シリカの作製

The goal of the protocols described herein is to synthesize bioinspired silica materials, perform enzyme encapsulation therein, and partially or totally ...

A Rapid Synthesis Method for Au, Pd, and Pt Aerogels Via Direct Solution-Based Reduction

Here, a method to synthesize gold, palladium, and platinum aerogels via a rapid, direct solution-based reduction is presented. The combination of various precursor noble metal ions with reducing agents in a 1:1 (v/v) ratio results in the formation of metal gels within seconds to minutes compared to much longer synthesis times for other techniques such as sol-gel. Conducting the reduction step in a microcentrifuge tube or small volume conical tube facilitates a proposed nucleation, growth, densification, fusion, equilibration model for gel formation, with final gel geometry smaller than the initial reaction volume. This method takes advantage of the vigorous hydrogen gas evolution as a by-product of the reduction step, and as a consequence of reagent concentrations. The solvent accessible specific surface area is determined with both electrochemical impedance spectroscopy and cyclic voltammetry. After rinsing and freeze drying, the resulting aerogel structure is examined with scanning electron microscopy, X-ray diffractometry, and nitrogen gas adsorption. The synthesis method and characterization techniques result in a close correspondence of aerogel ligament sizes. This synthesis method for noble metal aerogels demonstrates that high specific surface area monoliths may be achieved with a rapid and direct reduction approach.

A rapid, direct solution-based reduction synthesis method to obtain Au, Pd, and Pt aerogels is presented.

Au、Pd、およびソリューションに基づく還元を介して Pt エアロゲルの迅速合成法

Here, a method to synthesize gold, palladium, and platinum aerogels via a rapid, direct solution-based reduction is presented. The combination of various ...

Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source

Herein is presented a general strategy to perform reactions under mild to moderate CO2 pressures with dry ice. This technique obviates the need for specialized equipment to achieve modest pressures, and can even be used to achieve higher pressures in more specialized equipment and sturdier reaction vessels. At the end of the reaction, the vials can be easily depressurized by opening at room temperature. In the present example CO2 serves as both a putative directing group as well as a way to passivate amine substrates, thereby preventing oxidation during the organometallic reaction. In addition to being easily added, the directing group is also removed under vacuum, obviating the need for extensive purification to remove the directing group. This strategy allows the facile &#947;-C(sp3)-H arylation of aliphatic amines and has the potential to be applied to a variety of other amine-based reactions.

Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source

Here we present a protocol for performing reactions in simple reaction vessels under low-to-moderate pressures of CO2. The reactions can be performed in a variety of vessels simply by administering the carbon dioxide in the form of dry ice, without the need for costly or elaborate equipment or set-ups.

固体 CO2発生源としてドライアイスを使用して密閉容器で適度な圧力を達成します。

Herein is presented a general strategy to perform reactions under mild to moderate CO2 pressures with dry ice. This technique obviates the need for ...